Heterocyclic phosphorus-containing compounds and their production



.being a particularly potent insecticide.

United States inirnnocvcrro 'PHOSPHORUS-CQNTAINING comer-mos THEIR PRODUCTION William M. Lanham, Charleston, W. Va, assignor to Union Carbide Corporation, a corporation of New 'York g No Drawing, Application January 7, 1957 Serial No. 632,666

12 Claims. (Cl. 260-461) CH-O whereinR designates a member of the class consisting of hydrogen and the phenyl and lower alkyl radicals; {R' designates a member of the class consisting of hydrogen,

chlorine, bromine, and the phenyl and benzyl radicals;

R designates a member of the class consisting of hydrogen, chlorine, bromine, and the lower alkyl radicals; R designates a member of the class consisting of hydrogen and the phenyl radical; and at least one of the members of the group R, R and R is an aryl hydro carbon :substituent; X is a member of the class consisting of oxygen and sulfur; Y is a member of the class consisting of the chlorine, bromine, fluorine and mercapto radicals; and when Y is mercapto, X represents sulfur.

The novel compounds wherein Y represents a halogen .aregood insecticides, that-produced in Example II herein Moreover, the novel compounds of-the' invention wherein Y is mercapto and .X represents sulfur are usefulintermediates for the production of various new compounds by reaction with :aldehydes, ethylenically unsaturated carboxylic acids, .esters .and amides, epoxides, -alpha,'beta-olefinically unsaturated ketones, ethers, etc., having utility as insecticides. These compounds of the invention also have utility as promoters in the flotation of sulfide ores, and as lubricating oil additives. The new compounds wherein "Y is chlorine, bromine and fluorine also react with .aliphaticalcohols, phenols, and the alkali metal salts of alcohols and phenols, amines, and ammonia to produce neutral esters which are useful as pesticides, corrosion inhibitors, and petroleum oil additives. Thus, 5,5-dichloro 2 ethoxy 2 oxo 4 phenyl 1,3,2 dioxaphosphorinane was effective against Mexican bean beetle larvae when an aqueous solution containing 50 mg. of the compound per 100 cc. of the solution was sprayed upon bean plants which were then infested with the larvae and exposed for 7 2 hours.

The compounds of the invention wherein Y represents a mercapto group and X represents sulfur are relativelystrong acids, and are valuable intermediates for the production of various neutral compounds useful as pesticides, plasticizers, lubricating oil additives, etc. by reacting such compounds with 'alpha,beta-olefinically unsaturated esters, ethers,ketones,amides and with epoxides and aldehydes. Moreover, the compounds are useful as intermediates for the production "of the aryl-substituted atent iii r 2,894,016 Patented July 7, 1

heterocyclic thiophosphoryl halides of this invention according to the equation:

i PSH 301, 2G i o1+ S1013 21101 0 .0 where G is the hydrocarbon residue of an aryl-substituted 1,3-alkanediol.

'The novel compounds of the invention where Y repre} sents a halogen can'be prepared 'by reacting a phosphoryl halide or athiophos phoryl halide with an aryl-substituted :alkane-LB-diblof the structure nocmmcn'n cnn ori wherein R, R, R and R have the meanings previously indicated. Representative aryl-substituted alkane-1,3- diols useful as starting materials in the process of this invention include, among others:

1-phenyl-1,3-propanediol 1-phenyl-1,3-butanediol 1-phenyl-1,3-decanediol 1-phenyl-1,3-hexanedio1 2-ethy1-1-phenyl-1,3-butanedio1 Z-n-butyl-1 phenyl-1,3-butanediol 2-n-heptyl-1-pheny1-l,S-butanediol 2-benzyl-1-phenyl-1,3-butanediol l,3-diphenyl-2-ethyl-l,3-propanedio1 *1,B-diphenyLLB-propanediol 2,2 dichloro-l-phenyl-l,S-propanediol 2-phenyl-1,3-propanediol 2-benzyl- 1,3-propanediol 2-methyl-2-phenyl-1,3-propanediol '2-ethyl-2-ph'enyl-1,3-propanediol 2-butyl-2-phenyl-1,3-butanediol Z-methyI-Z-phenyl-1,3-hexanedio1 1-( 2,4,6-trimethy1phenyl) 1,3 -butanediol 2-ethyl-l-phenyFlB-hexanediol 2-butyl-l-phenyl-1,3-octanediol 2-heptyl-1-phenyl-1,3-hexanediol Z-benzyl-1-phenyl-1,3-hexanediol The diprimary aryl-substituted alkane-1,3-diols used as starting materials in the process of the invention can be made in Well known manner, as for example, by the method disclosed by Atkins et -al. in Iour. Am. Chem. Soc., vol. 70, p. 3121, involving the hydrogenation of an ester of an aryl-substituted malonic acid in the presence of a Raney nickel catalyst 'at around 150 C. and pressures around 5000 p.s.i.

The aryl-substituted a]kane-1,3-diols having both a primary hydroxyl and a secondary hydroxyl group, or having two secondary hydroxyl groups, useful as starting materials in the process, canbe made by the process described by Sprague et al. in Iour. Am. Chem. Soc., vol. 56, pp. 2669- (1934), involving the hydrogenation and hydrogenolysis of 1,3-diketones in dry ether with a Raney nickel catalyst under ISO-200 atmospheres pressure, at temperatures ranging from 50-60 C. to C.

The novel compounds of the invention wherein X represents sulfur and Y represents the mercapto radical can be prepared by reacting phosphorus penta sulfide with one of the before-described aryl-substitutedalkane- 1,3-diols according to the equation:

wherein- G represents the diol residue. In the production of these compounds where Y is a merca-pta-n radical it is customary to add slowly through a funnel the stoichiometric amount of powdered phosphorus pentasulfide to an agitated solution of the diol dissolved in xylene. However, the diol can be added to a suspension of the phosphorus pentasulfide in xylene. An excess of either reactant can be used, without adverse effect. While reaction temperatures'within the range from 25 to 125 C. are operative it is preferred to conduct the reaction at around 100 to 115 C. At temperatures above 125 C.

side reactions can occur to an objectionable extent. When the reaction is complete the reaction mixture becomes homogeneous and evolution of hydrogen sulfide ceases. The desired product can be purified by crystallizing from xylene, toluene or ethyl ether; or by preparing an aqueous solution of an alkali metal salt of the acid by reaction with an alkali metal hydroxide or carbonate, and filtering the solution, or extracting it with toluene, and then regenerating the desired product by the addition of a mineral acid such as hydrochloric acid.

The compounds of the invention wherein X represents sulfur or oxygen and Y represents a halogen can be made by reacting phosphoryl chloride or thiophosphoryl chloride, or the corresponding bromide or fluoride with one of the aforesaid aryl-substituted alkane-1,3-diols according to one of the equations.

/OH o P8013 zonnN OH O When using a thiophosphoryl halide as a reactant the preferred procedure is to add the diol, in solution in an inert solvent where the diol is a solid, dropwise into an agitated solution of an equimolar quantity of the thio phosphoryl halide in an inert solvent such as benzene, and the stoichiometric amount of a tertiary amine such as pyridine or triethylamine. Preferably reaction temperatures around 40 C. are used but temperatures around 25 to 60 C. areoperative. However, the thiophosphoryl halide can be added dropwise to an agitated solution of the diol in the pyridine and benzene. The reaction mixture then is filtered and washed with water to remove the last traces of the amine hydrochloride byproduct. In this manner a substantially pure residue product is secured in high yield. If desired, this product can be distilled under high vacuum, using a falling film type still.

In the production'of those compounds of the invention where X is oxygen and Y is a halogen, the reaction preferably is conducted at to C., by the addition of the diol, in solution in a solvent such as ethyl ether, to an equimolar quantity of a phosphoryl halide in the stoichiometric amount of pyridine and ethyl ether. If desired, the phosphoryl halide can be added dropwise to an agitated solution of the diol in pyridine and ethyl ether. Reaction temperatures in the range from around 50 C. to around +50 C. are operative. In place of ethyl ether any inert solvent can be used, such as ethylene dichloride, benzene, heptane, etc; These products are solids, and can be purified by crystallization. However, it is desirable first to remove the last traces of the amine hydrochloride by-product by washing with cold water.

If desired, the phosphoryl halidecan be added dropwise to a suspension ofthe diol in a volatile solvent such as benzene, ethyl ether, or a mixture thereof, while under vacuum, in the absence of a tertiary amine, as exemplified in Example IV. The reaction mixture then is stripped of solvent under high vacuum, and the residue product can be purified by crystallization from a filtered solution thereof in a'yolatile solvent such as a mixture of benzene andethylether. Y e

The following examples'will serve to illustrate thein- Y vention.

Example I To an agitated solution consisting of 0.5 mol of thiophosphoryl chloride, 1.0 mol of pyridine and 500 cc. of benzene held at 40 C. there were added dropwise during: twenty minutes 0.5 mol of 1-pheny1-1,3-propanediol.. After holding the reaction mixture at 40 C. for an additional two hours and allowing ittoset overnight 3.11125 C. it was filtered, and the resulting filtrate was washed with cold (10 C.) water, dried over calcium sulfate and filtered. This latter filtrate was stripped by distillation to a kettle temperature of 50 C. under less than 2 mm. of mercury pressure. There was thus obtained 110.5- grams of 2-chloro-4-phenyl-2-thiono-1,3,2-dioxaphosphorinane in the form of a yellow liquid residue having the following properties: percent purity (by esterification) 96.3; n30/D=l.5852. It had the following analysis,. in percent by weight: P=12.19; S=12.0; C=45.67;

H=4.66; percent yield, based upon the phosphoryl-con taining reactant=89.

Example II To an agitated solution consisting of 0.241 mol of 2'- methyl-Z-pheuyl-l,3-propanediol, 125 grams of benzene, 150 cc. of ethylene dichloride, and 0.50 mol of pyridine, held at 40 C. there were added dropwise during fifteen minutes 0.241 mol of thiophosphoryl chloride. After an additional two hours at 40 C. the reaction mixture was cooled to 10 C., filtered, and the residue washed with ethyl ether. The filtrate and ether washings were mixed and the mixture was washed with dilute aqueous sodium bicarbonate, washed with water until only slightly basic toward litmus, dried over calcium sulfate, cooled to 10"' C. and filtered. The filtrate was stripped by distillation at 25 C. under 10 mm. of mercury, and the mushy solid thus obtained was dissolved in ethyl ether, cooled to 40" C. and filtered. These two crystallizations yielded a waxy solid which, after stripping at 50 C.. under less than 1 mm. of mercury, yielded 36.5 grams. of a'dry, white solid, of which 27 grams was dissolved in a mixture of 125 cc. benzene and 100 cc. ethyl ether and recrystallized by cooling to 40 C. There was thus obtained 15 grams of Z-chloro-S-methyl-SpheriyI-Z- thiono-1,3,2-dioxaphosphorinane as a White solid having the following analysis percent by weight: P=11.66

(theoretical=11.79); 8: 12.07 (theoretical: 12.21); Cl=13.37 (theoretical=13.50); C=46.11 (theoretical=45.73 H=4.62 (theoretical=4.61)

The filtrate from the latter crystallization was stripped by distillation at 50 C. under less than 1.2 mm. of mercury, yielding an additional 12"grams of the aforesaid compound as a white solid still residue having the following properties:

Percent purity (by esterification) =98.4; and the followinganalysis, in percent by weight: P=l1.61; 8:12.38; C=46.55; H=4.73.

This last-named product was highly 'eifective in the control of bean aphids, permitting a to control thereof upon spraying nasturtium plant-s infested with the bean aphids with an aqueous solution containing 35 mg. of the compound per 100 cc. of the aqueous solution. It was likewise highly effective inthe control of red spider mites and of army worms.

Example III during twenty minutes a solution of 0.66mol of l-phenyl- 1,3-propanedi0l' in 100 cc. of ethyl ether. After allowing 'the'reaction mixture to stand overnight at 25 C. it was filtered, and'the residue was agitated in 1.5 liters of ethylene dichloride and filtered. The 181 grams of residue was washed with 500 cc, ofethylene dichloride and again filtered. The filtrates from the latter two filtrations were composited, and ,most of the ethylene dichloride was regamma :mjove'diby :distillation at 25 C. :under :less than v20 of mercury. The distillation residue subsequently :was ifiltered at .--'25 "C. The. resultant -:v'vhite ,solidgresi'dUe was added to'200-cc.1of ethyl etherv and filtered .at 10 C., and aSSJgramtp'ortiOn oftheresultant white'residue was .dissolved in 400 grams of ethyldichloride, washed withi5 C. water, :driedover calcium .sulfate filtered, and stripped by distillation at 25 C. under less thanaZ ofamercury. :Theresidue was washed at 25 IC. with-ethyl tether,- filtered, :and .jair dried to yield i2-'chloro -2.-oxo-4- phenyle-1 ,3g2edioxaphosphorinane :as a .white solid having the following properties: I

"Percent purity (by saponification) =99L2; I melting point='r1 1-2 -=1.13' C. (with decomposition); and the following analysis, in percent by weight:P '13.1'6 (theoretica1=l3.32); Cl=- .;14:44 (theoretical=l3.32); :45.94 (theoretical'=46.4'9); H=4I16 (theoretical=4.34).

qHs Example IV To an agitated-suspension ofi0.2'41 mol of 2-methy1-2- -phenyl-"1,3-propanedio1 in 1-50 grams of benzene and 70 grams of ethylether maintaineda't 25C. under 500 mm. of mercury pressure there were added dropwise during twenty-eight "minutes 0.241 mol-of phosphoryl chloride. Afterhea'ting the reaction mixture momentarily to 35 C.

it was maintained'at 25 C. -for 115 hours under 500 mm.

of mer'cury, the'n fo'r an hour'under 3 50mm; pressure and finally for an hour at less than 5 mm. of-m-ercury, all at 25 C. After stripping the reaction mixture by distillation to a kettle temperature of 50 C. under less than 2 mm. of -mercury the brown, mushy solid still residue was dissolvedin 100 cc. benzene at-40 C., diluted with 50 cc. ethyl ether, cooled to -'20 C. and filtered. The filtrate was stripped by distillation at 40 C. under 20 -ofmercury, cooled to 30 C. and filtered. The

- two filtrations yielded a white solid-residue which, after \GHPO/ is I a highly efie'ctive insecticide in the control of bean aphids.

Example V During [fifteen minutes "0.2 Smol of phosphorus pentarsulfide was-added in small successive portions to an agitated solution of 0.4 mol of 2,2-dichloro-1-phenyl-l;3- propanediol in 150 .cc. ofxylene'held at 100 C. After holding the'rea'ction mixture at 100 to 115 C. for-an 'hdditionalsixhours the evolution of hydrogen :sulfiderhad ceased. The reaction mixture was *filtered "at 11 15 -C. :and the filtrate was cooled vto 0 .C. and again filtered. The light brown residue from the latterfiltration was suspended in 150 ccuethylether,-cooled'-to 0 C. and filtered.

The resulting residue 'wasstripped by distillation ,at a

kettle temperature of 25 under ,less than v of mercury, yielding 5,5 dichloro-2-mercapto:4;phenyl 2-tlii- .ono-l ;3,2 dioxaphosphorinane in the form ofi-a tan solid residue having the following properties: percent purity (by acidity determination) =99.5;.melting point=l34 6 1137" It had the following analysis in percent by weight: P=l0.08 (theoretical=9.83); Cl=22.1'0 (theoretica1=22.48); S=20.2 (theoretical=20.33); C=34.4l (theoretical=34.30) .H=3.98 (theoretica1=2.88)

Q o 7 "i -s11 Exam le VI 2 :tmercapto --5 methyl 5-,phenyl i thi ono -.1,S,i-' dioxaphosphorinane-was prepared by the intermittent ad- -ditio'n 10f .22 ,g. -(0.1 mol) :of phosphorus pentasulfide to an agitated solution of '33 g. (0.2 mol) of Z-methyl-Z -.phenyl-1,3-.propanediol-h1 200cc. of toluene overa period of 114 minutes.

It was necessary to heat the reaction mixture :throughoutthis addition in order .to maintain the reaction temperature at C. After the addition the reaction-mixture was kept at 7 0'87 C. for anadditional 8 hours, at which time the reaction mixture was homogeneous-andhydrogen sulfide was no longer being evolved.

Example VII To an agitated suspension of 0.25 mol of 2,2-dichlorol-phenyl-l,3propanediolin 400 cc. of benzene and 01506 mol of pyridine heldat 25 C. there were added during fifteen minutes dropwise 0.25 mol of phosphoryl chloride. After an additional exposure at 25 C. for '64 hours the reaction mixture was filtered and the solid residue was washed with 5 C. water until free from the chloride ion, and was then washed with ethyl ether and then stripped by distillation at a kettle temperature of 25 C. under less than 2 mm. of mercury. Thus was obtained a 49% yield of 2- oxo-4phenyl-2,5,5-trichlorol-,3.,2-dioxaphosphorinane in the form of a white solid powder melting at l59-172 C., and having the following analysis, in percent by weight: P=10.07; Cl='3-3.05;

By thepractice of this invention there has .now been made available for use as pesticides, as intermediates .for the preparation of plasticizers for synthetic resins, including polyvinyl chloridesand vinyl. chloride-containing polymers, and as corrosion inhibitors, petroleum additives and-flotation agents, a novel class of high boiling heterocyclic phosphorus-containing compounds having atleast one phenyl or 'benzyl radical connected with a carbon atom or atoms of the .heterocyclic ring, which class of compounds offers the advantages over aliphatic heterocyclic phosphorus-containing compounds in that they are particularly resistant toward hydrolysis as evidenced by the fact that they can lac-washed with water.

The invention is susceptible of modification within the scope of the appended claims.

What is claimed is:

1. As new compounds, aryl hydrocarbon-substituted hetetocyclic sphospliorusecontaining "compounds having at least one aryl hydrocarbon residue attached to a correwherein R designates a member of the class consisting of;

hydrogen and the phenyl and lower alkyl radicals; R designates a member of the class consisting of hydrogen, chlorine, bromine, and the phenyl and benzyl radicals;

--R designates a member of the class consisting'of hydrogen, chlorine, bromine, and the lower alkyl radicals; R designates a member of the class consisting of hydrogen and the phenyl radical; and at least one of the R, R and R is an aryl-hydrocarbon substituent; X is a member of the class consisting of oxygen and sulfur; and Y is a member of the class consisting of thechlorine, bromine, and

mercapto radicals; and when Y is mercaptof-X-represents sulfur.

2. 'As new compounds, aryl 'hydroca'rbon substituted heterocyclic phosphorus-containing chlorides having at least one aryl hydrocarbon residue attached to a carbon atom of the heterocyclic ring, and having the structure R wherein R designates a member of the class consisting of hydrogen and the phenyl and lower alkyl radicals; R designates a member of the class consisting of hydrogen, chlorine, bromine, and the phenyl and benzyl radicals; R designates a member of the class consisting of hydrogen, chlorine, bromine, and the lower alkyl radicals; R designates a member of the class consisting of hydrogen and the phenyl radical; and at least one of the R, R, and R3 is an aryl-hydrocarbon substituent.

3. As new compounds, aryl hydrocarbon-substituted heterocyclic phosphorus-containing chlorides having at least one aryl hydrocarbon residue attached to a carbon atom of the heterocyclic ring, and having the structure wherein R designates a member of the class consisting of hydrogen and the phenyl and lower alkyl radicals; R designates a member of the class consisting of hydrogen, chlorine, bromine, and the phenyl and benzyl radicals; R designates a member of the class consisting of hydrogen, chlorine, bromine, and the lower alkyl radicals; R designates a member of the class consisting of hydrogen and the phenyl radical; and at least one of the R, R, and R is an aryl hydrocarbon substituent.

4. As new compounds, aryl hydrocarbon-substituted heterocyclic phosphorus-containing compounds having at least one aryl hydrocarbon residue attached to a corresponding carbon atom of the heterocyclic ring, and having the structure hydrogen and the phenyl and lower alkyl radicals; R

7,8 designates a member of the class consisting of hydrogen, chlorine, bromine and the phenyl and benzyl radicals; R designates a member of the class consisting of hydrogen, chlorine, bromine, and the lower alkyl radicals; R

designates a member of the class consisting of hydrogen and theiphenyl radicals; and at least one of the members of the group R, R and R is an aryl hydrocarbon substituent. t

5. Process for making aryl hydrocarbon-substituted heterocyclic phosphorus-containing compounds which comprises reacting (1) a phosphorus compound of the class consisting of phosphorus. pentasulfide, phosphoryl chloride, phosphoryl bromide, thiophosphoryl chloride, and thiophosphoryl bromide with' (2) an aryl-substituted alkane-1,3-diol having the structure wherein R is of the class consisting of hydrogen and the phenyl and lower alkyl radicals; R is of the class consisting of hydrogen, chlorine, bromine, and the phenyl and benzyl radicals; R is of the class consisting of hydrogen, chlorine, bromine, and the lower alkyl radicals; and R is of the class consisting of hydrogen and the phenyl radicals; and at least one of the R, R and R is an arylhydrocarbon substituent; and separately recovering from the resultantreaction mixture the said aryl hydrocarbonsubstituted heterocyclic phosphorus-containing compound thus produced;

6. Process for making aryl hydrocarbon-substituted heterocyclic aliphatic phosphates, which comprises reacting thiophosphoryl chloride at temperatures within the range of from 25 to 60 C., with an aryl-substituted a1- kane 1,3-diol having the structure t wherein R is of the class consisting of hydrogen and the phenyl and lower alkyl radicals; R is of the class consisting of hydrogem'chlorine, bromine andthe phenyl and benzyl radicals; R isof the class consisting of hydrogen, chlorine, bromine, and the lower alkylradicalsrR? is of the class consisting of hydrogen and/the phenyl radical; and at least one of the R, R and R ;is an aryl hydrocarbon substituent; and separately recovering fromjhe'resultant reaction mixture the aryl hydrocarbon-substituted heterocyclic halothiono phosphate thus, produced. 3

7. Process for making aryl hydrocarbon-substituted heterocyclic phosphorus-containing compounds which comprises reacting phosphoryl chloride, at temperatures within the range of from around -5 0 ,C. to around +50 C., with an aryl-substituted 'alkane- 1,3rdiol having the structure H0CHRCR'R CHR 0H wherein R is of the class consisting of hydrogen and the phenyl and lower alkyl radicals; R is of the class consisting of hydrogen, chlorine, bromine, and the phenyl and benzyl radicals; R is of the class consisting of hydrogen, chlorine, bromine, and the lower alkyl radicals; and R is of the class consisting of hydrogen and the phenyl radical; and at least one of the R, R and R is an aryl-hydrocarbon substituent; and separately recovering from the resultant re action mixture the said aryl hydrocarbon-substituted heterocyclic phosphorus-containing compound thus produced.

8. Process for making aryl hydrocarbon-substituted heterocyclic dithiophosphoric acids, which comprises reacting phosphorus pentasulfide at temperatures within the range of from 25 to C. with an aryl-substituted alkane 1,3-diol, having thestructure Y HOCHRCR'RCHR- OH wherein R is of the class consisting of hydrogen and the phenyl and lower alkyl radicals; R is of the class consisting of hydrogen, chlorine, bromine, and the-phenyl and benzyl-radicals;'R is ofthe class consisting of hydrogen, chlorine, bromine, and the lower alkyl radicals; and R is of the class consisting of hydrogen and the phenyl radical; and at least one of the R, R and R is an andhydrocarbon substituent; and separately recovering from the resultant reaction mixture the said aryl hydrocarbonsubstituted heterocyclic dithiophosphoric acid thus produced.

9. As a new compound, 2-ch1oro-5-methy1-5-phenyl- Z-thiono-1,3,2-dioxaphosphorinane.

10 10. As a new compound, 2-chloro-4-pheny1-2-thiono- 1,3,2-dioxaphosphorinane.

11. As a new compound, 5,5-dich1oro-2-mercapto-4- phenyl-Z-thionm1,3,2-dioxaphosphorinane. 5 12. As a new compound, Z-mercapto-S-methyl-S- pheny1-2-thiono1,3,2-dioxaphosphorinane.

No references cited. 

1. AS NEW COMPOUNDS, ARYL HYDROCARBON-SUBSTITUTED HETEROCYCLIC PHOSPHORUS-CONTAINING COMPOUNDS HAVING AT LEAST ONE ARYL HYDROCARBON RESIDUE ATTACHED TO A CORRESPONDING CARBON ATOM OF THE THE HETEROCYCLIC RING, AND HAVING THE STRUCTURE
 5. PROCESS FOR MAKING ARYL HYDROCARBON-SUBSTITUTED HETEROCYCLIC PHOSPHORUS-CONTAINING COMPOUNDS WHICH COMPRISES REACTING (1) A PHOSPHORUS COMPOUND OF THE CLASS CONSISTING OF PHOSPHORUS PENTASULFIDE, PHOSPHORYL CHLORIDE, PHOSPHORYL BROMIDE, THIOPHOSPHORYL CHLORIDE, AND THIOPHOSPHORYL BROMIDE WITH (2) AN ARYL-SUBSTITUTED ALKANE-1,3-DIOL HAVING THE STRUCTURE 